CN115595618B - Copper-based monoatomic alloy electrocatalyst and preparation method and application thereof - Google Patents
Copper-based monoatomic alloy electrocatalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN115595618B CN115595618B CN202211322528.1A CN202211322528A CN115595618B CN 115595618 B CN115595618 B CN 115595618B CN 202211322528 A CN202211322528 A CN 202211322528A CN 115595618 B CN115595618 B CN 115595618B
- Authority
- CN
- China
- Prior art keywords
- copper
- metal precursor
- nano
- monoatomic
- noble metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/089—Alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/11—Halogen containing compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a copper-based monoatomic alloy electrocatalyst, a preparation method and application thereof, and relates to the technical field of monoatomic catalysts. According to the invention, cetyl trimethyl ammonium bromide is added into a reaction system, copper ions and cetyl trimethyl ammonium bromide are coordinated to form a plane triangle for controlling the morphology of the prepared nano copper sheet; the alkaline environment for preparing the nano copper sheet is provided by adding hexamethylenetetramine, under the heating condition, the (111) crystal face copper nano sheet is obtained, and finally noble metal single atoms are strongly anchored on the (111) crystal face of the copper nano sheet through galvanic replacement reaction, so that the stability of the catalyst is improved, and finally, the consumption of noble metal is reduced, and the catalytic capability of the catalyst is improved under the synergistic effect of the copper nano sheet and the noble metal.
Description
Technical Field
The invention relates to the technical field of monoatomic catalysts, in particular to a copper-based monoatomic alloy electrocatalyst, and a preparation method and application thereof.
Background
The halogenated organic matters have the risks of cancerogenesis, teratogenesis, mutation and the like, enter the water environment, and bring great hidden trouble to human health. The electrocatalytic reduction technology is a green chemical process, can realize the detoxication of halogenated organic pollutants by consuming water and electrons, and has the advantages of high efficiency, strong economy, flexible operation and convenient amplification.
The key to electrocatalytic reduction technology is to design the electrocatalyst needed to synthesize the electrode material. The electrocatalyst commonly used in the prior art is mainly noble metal (such as palladium, platinum and the like), and is loaded on a carbon electrode to prepare an electrode for electrocatalytic reduction of halogenated organic matters. Although the electrode material obtained by the method has good electrocatalytic reduction halogenated organic performance, the electrode material is prepared by directly loading noble metal on a carbon electrode, and the required noble metal dosage is large.
Therefore, there is a need to provide a method for preparing an electrocatalyst with low noble metal consumption and high efficiency in electrocatalytic reduction of halogenated organics.
Disclosure of Invention
In view of the above, the invention aims to provide a copper-based monoatomic alloy electrocatalyst, and a preparation method and application thereof. The copper-based monoatomic alloy electrocatalyst obtained by the preparation method provided by the invention not only reduces the consumption of noble metal, but also has higher efficiency of electrocatalytic reduction of halogenated organic matters and higher stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a copper-based monoatomic alloy electrocatalyst, which comprises the following steps:
(1) Mixing water, a copper metal precursor, a reducing agent, hexadecyl trimethyl ammonium bromide and hexamethylenetetramine to obtain a mixed solution;
(2) Heating the mixed solution obtained in the step (1) to perform a reduction reaction to obtain copper nano sheets;
(3) Mixing the copper nano-sheets obtained in the step (2) with water to obtain a copper nano-sheet aqueous solution;
(4) And (3) adding a noble metal precursor into the copper nano sheet aqueous solution obtained in the step (3) in an inert atmosphere to perform a galvanic couple replacement reaction, so as to obtain the copper-based monoatomic alloy electrocatalyst.
Preferably, the copper metal precursor in the step (1) includes at least one of copper chloride, copper nitrate, copper sulfate, copper chloride hydrate, copper nitrate hydrate, and copper sulfate hydrate; the reducing agent includes at least one of ascorbic acid, glucose, hydrazine hydrate and sodium borohydride.
Preferably, in the step (1), the mass ratio of the copper metal precursor to the reducing agent is 1: (1.8-2.5).
Preferably, the mass ratio of the hexadecyl trimethyl ammonium bromide to the hexamethylenetetramine in the step (1) is 1 (0.8-1.2); the mass ratio of the cetyl trimethyl ammonium bromide to the copper metal precursor in the step (1) is (1.8-2.5): 1.
preferably, the temperature of the reduction reaction in the step (2) is 60-100 ℃, and the time of the reduction reaction is 0.5-5 h.
Preferably, the mass-to-water volume ratio of the copper nano-sheets in the step (3) is 10mg: (15-25) mL.
Preferably, the noble metal precursor in the step (4) includes at least one of palladium nitrate, chloroplatinic acid and chloroauric acid.
Preferably, in the step (4), the molar ratio of the noble metal precursor to the copper nanoplatelets in the mixed solution C is 1: (1-500).
The invention provides the copper-based monoatomic alloy electrocatalyst prepared by the preparation method, wherein the carrier of the copper-based monoatomic alloy electrocatalyst is a copper nano sheet; the copper nano sheet is in a regular triangle copper nano sheet or a hexagon copper nano sheet, the crystal face of the copper nano sheet is mainly a (111) crystal face, and the thickness of the copper nano sheet is 1-10 nm.
The invention also provides application of the copper-based monoatomic alloy electrocatalyst in electrocatalytic reduction of halogenated organics.
The invention provides a preparation method of a copper-based monoatomic alloy electrocatalyst, which comprises the following steps: (1) Mixing water, a copper metal precursor, a reducing agent, hexadecyl trimethyl ammonium bromide and hexamethylenetetramine to obtain a mixed solution; (2) Heating the mixed solution obtained in the step (1) to perform a reduction reaction to obtain copper nano sheets; (3) And (3) mixing the copper nano sheet obtained in the step (2), water and a noble metal precursor in an inert atmosphere to perform a galvanic couple replacement reaction, so as to obtain the copper-based monoatomic alloy electrocatalyst. In the invention, under the heating condition, a copper metal precursor is firstly reduced into monovalent copper ions by a reducing agent, and then the monovalent copper ions are reduced into copper simple substances to obtain nano copper; the surface active agent cetyl trimethyl ammonium bromide is added into the reaction system, and copper ions and cetyl trimethyl ammonium bromide are coordinated to form a plane triangle for controlling the morphology of the prepared nano copper sheet; the addition of hexamethylenetetramine provides an alkaline environment for preparing nano copper sheets, and simultaneously hexadecyl trimethyl ammonium bromide and hexamethylenetetramine are matched for use, so that the effect of stabilizing monovalent copper ions can be achieved; finally, utilizing the potential difference between the copper simple substance in the copper nano sheet and the noble metal ion in the noble metal precursor in the solution system to carry out galvanic couple replacement reaction to obtain the copper-based monoatomic alloy electrocatalyst; the preparation method provided by the invention has the advantages of high specific surface area and high conductivity, so that the number of active sites of the electrocatalyst can be increased, the current is enhanced, the reaction rate is improved, meanwhile, metallic copper can also effectively inhibit the hydrogen evolution reaction of a cathode in the electrocatalytic reaction, and metallic palladium can effectively realize debromination hydrogenation, and the synergistic coupling of the two components promotes the electrocatalytic dehalogenation of halogenated organic matters, meanwhile, because the electrocatalyst provided by the invention is in a positive reducing potential in the cathode reaction, the occurrence of hydrogen evolution side reaction can be reduced, and the mass transfer blockage caused by the hydrogen evolution reaction is inhibited, so that the current efficiency and the catalytic activity are comprehensively improved, and the stronger catalytic stability is maintained; and the preparation method provided by the invention is utilized, the obtained copper nano-sheet takes the (111) crystal face as a main part, at this time, palladium monoatoms are strongly anchored on the (111) crystal face of the copper nano-sheet, and the palladium monoatoms can be prevented from falling off during the electrocatalytic reaction, so that the stability of the electrocatalyst is further improved. Experimental results show that the catalytic efficiency can reach 100% when the electrocatalyst provided by the invention is used for electrocatalytically reducing tribromophenol, and the degradation performance of the tribromophenol can be maintained at 100% after 8 times of circulation.
Drawings
FIG. 1 is a schematic diagram of a copper-based monoatomic alloy electrocatalyst Pd according to example 1 of the invention 0.06 Transmission Electron Microscope (TEM) images of Cu SAAs;
FIG. 2 is a schematic diagram of a copper-based monoatomic alloy electrocatalyst Pd according to example 1 of the invention 0.06 X-ray diffraction (XRD) patterns of Cu SAAs;
FIG. 3 is a schematic diagram of a copper-based monoatomic alloy electrocatalyst Pd according to example 1 of the invention 0.06 Cu SAAs Selected Area Electron Diffraction (SAED) patterns;
FIG. 4 shows a copper-based monoatomic alloy electrocatalyst Pd according to example 1 of the invention 0.06 Cu SAAs spherical aberration correction high-angle annular dark field scanning transmission electron microscope (Cs-HAADF-STEMSAED) images;
FIG. 5 is a schematic diagram of a copper-based monoatomic alloy electrocatalyst Pd according to example 1 of the invention 0.06 Cu SAAs, comparative example 1 prepared copper nanoparticles CuNPs, purchased palladium nanoparticles PdNPs, purchased copper nanosheets CuNSs respectively to the comparison graph of the electrocatalytic degradation performance of tribromophenol;
FIG. 6 shows the present inventionCopper-based monoatomic alloy electrocatalyst Pd prepared in example 1 0.06 Distribution graphs of Cu SAAs degradation performance on tribromophenol and intermediate products over time;
FIG. 7 shows a copper-based monoatomic alloy electrocatalyst Pd according to example 1 of the invention 0.06 Stability test pattern of Cu SAAs against electrocatalytic degradation of tribromophenol.
Detailed Description
The invention provides a preparation method of a copper-based monoatomic alloy electrocatalyst, which comprises the following steps:
(1) Mixing water, a copper metal precursor, a reducing agent, hexadecyl trimethyl ammonium bromide and hexamethylenetetramine to obtain a mixed solution;
(2) Heating the mixed solution obtained in the step (1) to perform a reduction reaction to obtain copper nano sheets;
(3) Mixing the copper nano-sheets obtained in the step (2) with water to obtain a copper nano-sheet aqueous solution;
(4) And (3) adding a noble metal precursor into the copper nano sheet aqueous solution obtained in the step (3) in an inert atmosphere to perform a galvanic couple replacement reaction, so as to obtain the copper-based monoatomic alloy electrocatalyst.
The invention mixes water, copper metal precursor, reducer, hexadecyl trimethyl ammonium bromide and hexamethylenetetramine to obtain mixed solution.
In the present invention, the copper metal precursor preferably includes at least one of copper chloride, copper nitrate, copper sulfate, copper chloride hydrate, copper nitrate hydrate, and copper sulfate hydrate, more preferably copper nitrate hydrate. The invention takes the substances as copper metal precursors, which can be fully dissolved in water to provide the required bivalent copper ions.
In the present invention, the reducing agent preferably includes at least one of ascorbic acid, glucose, hydrazine hydrate and sodium borohydride, and more preferably ascorbic acid. The invention takes the substances as the reducing agent, which is favorable for reducing cupric ions into monovalent copper ions.
In the present invention, the water is preferably deionized water. The invention adopts deionized water, which can avoid the adverse effect of impurity ions in water on the preparation of copper nano-sheets.
In the invention, the mass ratio of the copper metal precursor to the reducing agent is preferably 1: (1.8 to 2.5), more preferably 1:2. The invention limits the dosage of the copper metal precursor and the reducer in the above range, which is beneficial to the final conversion of bivalent copper ions into copper simple substance.
The amount of water used in the present invention is not particularly limited, and may be conventionally added by using the amount of a solvent well known to those skilled in the art.
In the present invention, the mixing sequence of the water, the copper metal precursor, the reducing agent, the cetyl trimethylammonium bromide and the hexamethylenetetramine is preferably that the water and the copper metal precursor are mixed first and then sequentially mixed with the reducing agent, the cetyl trimethylammonium bromide and the hexamethylenetetramine.
In the present invention, the mixing is preferably performed under stirring. The stirring mode is not particularly limited, and stirring modes well known to those skilled in the art are adopted, so that materials are fully contacted. According to the invention, the reducing agent is added before the hexadecyl trimethyl ammonium bromide and the hexamethylenetetramine are added, so that the divalent copper ions in the copper metal precursor are reduced into the copper simple substance gradually; and the subsequent addition of the cetyl trimethyl ammonium bromide is favorable for the sufficient coordination of the cetyl trimethyl ammonium bromide and copper ions to form a plane triangle, thereby being favorable for controlling the morphology of the prepared nano copper sheet.
In the present invention, the mass ratio of the cetyl trimethylammonium bromide to the hexamethylenetetramine is preferably 1 (0.8 to 1.2), more preferably 1:1. In the present invention, the mass ratio of the cetyltrimethylammonium bromide to the copper metal precursor is preferably (1.8 to 2.5): 1, more preferably 2:1. The invention limits the dosage of the hexadecyl trimethyl ammonium bromide and the hexamethylenetetramine in the range, is favorable for fully coordinating the hexadecyl trimethyl ammonium bromide and monovalent copper ions obtained after the reduction reaction to form a plane triangle, thereby being favorable for controlling the morphology of the prepared nano copper sheet; wherein hexamethylenetetramine provides the alkaline environment required for preparing the nano-copper sheet.
After the mixed solution is obtained, the mixed solution is heated to perform a reduction reaction, and the copper nano-sheet is obtained.
In the present invention, the temperature of the reduction reaction is preferably 60 to 100 ℃, more preferably 70 to 90 ℃; the time of the reduction reaction is preferably 0.5 to 5 hours, more preferably 1 to 4 hours. In the present invention, the temperature rise rate of the reduction reaction is preferably 1 to 12℃min –1 More preferably 1 to 5℃min –1 . The invention limits the temperature, time and heating rate of the reduction reaction in the above range, which is beneficial to fully converting copper ions into copper simple substance.
After completion of the reduction reaction, the present invention preferably sequentially subjects the product of the reduction reaction to centrifugation and washing.
The method has no special regulation on the centrifugal mode, and the solid-liquid separation is realized by adopting a conventional centrifugal mode.
In the present invention, the washing reagent is preferably a solution of alcohol and water, more preferably an aqueous solution of ethanol. The ratio of the ethanol to the water in the ethanol aqueous solution is not particularly limited, and any ratio can be used. The washing mode is not particularly limited in the present invention, and impurities contained in the solid product may be washed away by washing modes well known to those skilled in the art.
After the washing is completed, the washed copper nano-sheets are preferably stored.
In the present invention, the process of preservation is preferably dispersing the copper nanoplatelets in an ethanol solution, and in the present invention, the mass concentration of the ethanol solution is preferably 95%. According to the invention, the copper nano-sheets are dispersed in the ethanol solution, so that the copper nano-sheets can be prevented from being oxidized by air.
After the copper nano-sheet is obtained, the copper nano-sheet is mixed with water to obtain the copper nano-sheet aqueous solution.
The copper nanoplatelets are preferably subjected to a drying pretreatment prior to mixing. In the present invention, the drying means is preferably vacuum drying. In the present invention, the temperature of the vacuum drying is preferably 55 to 65 ℃, and the time of the vacuum drying is preferably 5 to 7 hours. The vacuum degree of the vacuum drying is not specially defined, and the vacuum degree is selected conventionally. The method adopts a vacuum drying mode to dry, so that the oxidation of oxygen in the air to the copper nano-sheets can be avoided. The invention limits the temperature and time of the vacuum drying to the above range, and can realize the full drying of the copper nano-sheets. The method can remove the solvent ethanol solution during the preservation of the copper nano-sheets by drying, and avoid the adverse effect of the solvent ethanol on the prepared electrocatalyst.
In the present invention, the means of mixing the copper nanoplatelets and water is preferably ultrasound. The invention has no special regulation on the frequency and time of the ultrasonic wave, and the ultrasonic wave frequency and time which are well known to the person skilled in the art are adopted to realize the full mixing of materials.
In the invention, the mass and water volume ratio of the copper nano-sheet is preferably 10mg: (15-25) mL, more preferably 10mg:20mL. The invention limits the dosage of the copper nano-sheet and water in the above range, can realize that the copper nano-sheet is fully dispersed in water, and is favorable for the follow-up galvanic reaction.
After the copper nano-sheet aqueous solution is obtained, the noble metal precursor is added into the copper nano-sheet aqueous solution under the inert atmosphere to carry out the galvanic couple replacement reaction, so as to obtain the copper-based monoatomic alloy electrocatalyst.
In the present invention, the noble metal precursor preferably includes at least one of palladium nitrate, chloroplatinic acid, and chloroauric acid, more preferably palladium nitrate. The noble metal precursor is used as the noble metal precursor, so that the noble metal precursor is fully dissolved in water and the copper nano-sheet is subjected to galvanic replacement reaction, and the noble metal simple substance is anchored on the copper nano-sheet.
In the present invention, the noble metal precursor is preferably added in the form of an aqueous solution. According to the invention, the noble metal precursor is dissolved in water, so that the galvanic replacement reaction of noble metal ions in the noble metal precursor and the copper simple substance in the copper nano sheet is facilitated.
In the invention, the molar ratio of the noble metal atoms in the noble metal precursor to the copper atoms in the copper nano-sheets in the mixed solution C is preferably 1: (1 to 500), more preferably 1: (10-20). In the present invention, the concentration of the aqueous solution of the noble metal precursor is preferably (0.8 to 1.2) g/L, more preferably 1.0g/L. The amount of the aqueous solution of the noble metal precursor is not particularly limited, and the molar ratio of the noble metal atoms in the noble metal precursor to the copper atoms in the copper nano-sheets in the mixed solution C can be satisfied.
In the present invention, the galvanic replacement reaction is preferably carried out under stirring. In the present invention, the stirring time is preferably 0.1 to 5 hours. In the present invention, the stirring time is preferably a time taken from the addition of the noble metal precursor to the end of stirring. The stirring mode is not particularly limited, and materials of the reaction system are fully mixed by adopting a stirring mode well known to a person skilled in the art. The stirring time is limited to the above range, which is favorable for fully carrying out the galvanic replacement reaction.
After the stirring is completed, the stirred product is preferably subjected to centrifugation, washing and drying in sequence, so that the copper-based monoatomic alloy electrocatalyst is obtained.
The invention has no special regulation on the operation of centrifugation, and can realize solid-liquid separation by adopting a conventional centrifugation mode.
In the present invention, the washing reagent is preferably deionized water and ethanol. The method for washing is not particularly limited, and the reagent is adopted to sufficiently wash the impurities on the solid product obtained after centrifugation.
In the present invention, the drying means is preferably vacuum drying. In the present invention, the temperature of the vacuum drying is preferably 55 to 65 ℃, and the time of the vacuum drying is preferably 5 to 7 hours. The vacuum degree of the vacuum drying is not specially defined, and the vacuum degree is selected conventionally. According to the invention, the copper nano-sheets in the copper-based monoatomic alloy electrocatalyst can be prevented from being oxidized by oxygen in the air by selecting a vacuum drying mode for drying; by limiting the temperature and time of the vacuum drying to the above ranges, sufficient drying of the copper nanoplatelets can be achieved.
In the present invention, the inert atmosphere gas is preferably nitrogen or argon. The invention carries out the couple replacement reaction under the inert atmosphere, and can avoid the adverse effect of oxygen in the air on the couple replacement reaction.
According to the preparation method of the copper-based monoatomic alloy electrocatalyst, provided by the invention, the noble metal monoatoms are strongly anchored on the crystal face of the copper nanosheet (111) through the galvanic couple replacement reaction, so that the consumption of noble metals is reduced, the noble metal monoatoms are prevented from falling off during the electrocatalyst reaction, and the stability of the electrocatalyst is further improved.
The invention provides the copper-based monoatomic alloy electrocatalyst prepared by the preparation method. In the present invention, the carrier of the copper-based monoatomic alloy electrocatalyst is preferably a copper nanoplatelet. In the present invention, the shape of the copper nanoplatelets is preferably a regular triangle copper nanoplatelet or a hexagonal copper nanoplatelet. In the present invention, the crystal plane of the copper nanoplatelets is preferably mainly a (111) crystal plane. In the present invention, the thickness of the copper nanoplatelets is preferably 1 to 10nm.
The invention also provides application of the copper-based monoatomic alloy electrocatalyst in electrocatalytic reduction of halogenated organics.
The invention has no special regulation on the application, and the copper-based monoatomic alloy electrocatalyst is loaded on a carbonaceous electrode to prepare the electrode by adopting an application method well known to a person skilled in the art, and then the electrode is used for electrocatalytically reducing halogenated organic matters in water. In the present invention, the halogenated organic compound is preferably tribromophenol. In the present invention, the concentration of the tribromophenol is preferably 8 to 12mg/L, more preferably 10mg/L.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the copper-based monoatomic alloy electrocatalyst comprises the following steps:
(1) Mixing water, a copper metal precursor, a reducing agent, hexadecyl trimethyl ammonium bromide and hexamethylenetetramine to obtain a mixed solution; the specific operation is as follows: under the stirring condition, firstly mixing 15.0mL of deionized water with 50mg of copper metal precursor copper nitrate trihydrate, and then sequentially adding 100mg of reducing agent ascorbic acid, 100mg of cetyltrimethylammonium bromide and 100mg of hexamethylenetetramine to obtain a mixed solution;
(2) Heating the mixed solution obtained in the step (1) to perform a reduction reaction to obtain copper nano sheets;
the specific operation is as follows: raising the temperature of the obtained mixed solution to 80 ℃ at a heating rate of 2 ℃/min, reacting for 3 hours, then sequentially centrifuging and washing to obtain copper nano-sheets, dispersing the copper nano-sheets into an ethanol solution with the mass fraction of 95%, and preserving the copper nano-sheets; wherein the washing reagent is a mixed solution of ethanol and water (volume ratio is 1:1);
(3) Mixing the copper nano-sheets obtained in the step (2) with water to obtain a copper nano-sheet aqueous solution; the specific operation is as follows: firstly, carrying out vacuum drying on copper nano sheets for 6 hours at 60 ℃, and then carrying out ultrasonic mixing on 10mg of dried copper nano sheets and 20mL of deionized water to obtain copper nano sheet aqueous solution, wherein the copper nano sheet aqueous solution is pink quicksand suspension;
(4) Adding a noble metal precursor into the copper nano sheet aqueous solution obtained in the step (3) in an inert atmosphere to perform a galvanic couple replacement reaction to obtain a copper-based monoatomic alloy electrocatalyst; the specific operation is as follows: under the protection of argon, under the condition of continuously stirring, adding 2.621mL (Pb: cu molar ratio is 1:16) of palladium nitrate precursor aqueous solution with the noble metal precursor concentration of 1.0g/L into the copper nano-sheet aqueous solution, performing galvanic replacement reaction, and then sequentially centrifuging, washing and drying to obtain the copper-based monoatomic alloy electrocatalyst which is named Pd 0.06 Cu SAAs, wherein SAAs represents a single atom electrocatalyst;
wherein the stirring time is 30min, and the stirring time at this time refers to the total time taken from the addition of the noble metal precursor to the end of stirring; the washed reagent is deionized water and ethanol; the drying is vacuum drying, the drying temperature is 60 ℃, and the drying time is 12 hours.
Comparative example 1
The preparation method of the copper nano sheet comprises the following steps:
(1) Mixing water, a copper metal precursor, a reducing agent, hexadecyl trimethyl ammonium bromide and hexamethylenetetramine to obtain a mixed solution; the specific operation is as follows: under the stirring condition, firstly mixing 15.0mL of deionized water with 50mg of copper metal precursor copper nitrate trihydrate, and then sequentially adding 100mg of cetyltrimethylammonium bromide and 100mg of hexamethylenetetramine to obtain a mixed solution;
(2) Heating the mixed solution obtained in the step (1) to perform a reduction reaction to obtain copper nano sheets;
the specific operation is as follows: raising the temperature of the obtained mixed solution to 80 ℃ at the rate of 2 ℃/min, reacting for 3 hours, and then sequentially centrifuging, washing and drying to obtain copper nano-sheets, which are marked as CuNSs;
wherein the washing reagent is a mixed solution of ethanol and water (volume ratio is 1:1); the drying is vacuum drying, the drying temperature is 60 ℃, and the drying time is 12 hours.
FIG. 1 is a Pd prepared in example 1 of the present invention 0.06 Transmission Electron Microscope (TEM) images of Cu SAAs, pd can be seen from fig. 1 0.06 Cu SAAs exist in the form of regular triangular nanoplatelets.
FIG. 2 is a schematic diagram of a copper-based monoatomic alloy electrocatalyst Pd according to example 1 of the invention 0.06 X-ray diffraction (XRD) patterns of Cu SAAs; pd can be seen from FIG. 2 0.06 Cu SAAs is mainly composed of (111) crystal planes.
FIG. 3 is a schematic diagram of a copper-based monoatomic alloy electrocatalyst Pd according to example 1 of the invention 0.06 Cu SAAs Selected Area Electron Diffraction (SAED) patterns; pd can be seen from FIG. 3 0.06 Cu SAAs exhibits a face-centered cubic structure along the (111) direction.
FIG. 4 shows a copper-based monoatomic alloy electrocatalyst Pd according to example 1 of the invention 0.06 Cu SAAs spherical aberration correction high-angle annular dark field scanning transmissionElectron microscope (Cs-HAADF-stem aed) images; pd can be seen from FIG. 4 0.06 Palladium in Cu SAAs exists as a single atom on the surface of copper nanoplatelets.
Electrocatalytic reduction of halogenated organics experiments:
preparing standard solutions of tribromophenol/dibromophenol/monobromophenol/phenol, measuring peak areas of various substances at different concentrations by utilizing high performance liquid chromatography, and respectively obtaining working curves of different substances by linear fitting.
The performance test uses an H-type electrolytic cell, and the working electrode is 2 x 2cm of the supported electrocatalyst 2 Carbon paper with 2 x 2cm counter electrode 2 The platinum net and the reference electrode are saturated calomel electrodes.
Experimental conditions: ph=4 (phosphate buffer), concentration of tribromophenol=10 mg/L, potential= -0.6vvs.sce, reaction time=4 h.
Taking a certain amount of reaction solution at different reaction times, passing through a 0.22 mu m filter membrane, and then performing high performance liquid chromatography test to obtain the concentrations of different products/reactants at different reaction times according to the peak areas of the corresponding substances and the established working curves.
Experimental results:
HPLC analysis parameters for six target contaminants are shown in Table 1
TABLE 1 HPLC analysis parameters for six target pollutants
Among them, 2,4, 6-tribromophenol (2, 4, 6-TBP), phenol (Phenols), 2, 6-dibromophenol (2, 6-DBP), 2, 4-dibromophenol (2, 4-DBP), 2-bromophenol (2-BP) and 4-bromophenol (4-BP).
As can be seen from Table 1, the peak area and concentration relationships of six target contaminants at different concentrations are strongly linearly related, the fitting Relative Standard Deviation (RSD) is small, and the R square value (R 2 ) Near 1, the fitting accuracy is higher.
FIG. 5 is a schematic diagram of a copper-based monoatomic alloy electrocatalyst Pd according to example 1 of the invention 0.06 Cu SAAs pairCopper nanosheets cuss prepared in proportion 1; the comparison chart of the electrocatalytic degradation performance of the purchased copper nano-particles CuNPs and the purchased palladium nano-particles PdNPs to tribromophenol respectively; pd can be seen from FIG. 5 0.06 Cu SAAs can be completely degraded within 4 hours by 10mg L- 1 The catalytic dehalogenation reduction performance of the comparative sample CuNPs/CuNSs/PdNPs on the tribromophenol is poor, and the degradation rate is less than 40% after 4 hours.
FIG. 6 is a schematic diagram of a copper-based monoatomic alloy electrocatalyst Pd according to example 1 of the invention 0.06 Distribution graphs of Cu SAAs degradation performance on tribromophenol and intermediate products over time; pd can be seen from FIG. 6 0.06 The degradation products of Cu SAAs include Phenol (Phenols), 2, 6-dibromophenol (2, 6-DBP), 2, 4-dibromophenol (2, 4-DBP), 2-bromophenol (2-BP) and 4-bromophenol, wherein the selectivity to Phenols can reach more than 90%.
FIG. 7 shows a copper-based monoatomic alloy electrocatalyst Pd according to example 1 of the invention 0.06 Stability test chart of Cu SAAs for electrocatalytic degradation of tribromophenol; pd can be seen from FIG. 7 0.06 The Cu SAAs has extremely high stability, and the degradation performance of the p-tribromophenol after 8 times of circulation can be kept at 100%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (4)
1. The preparation method of the copper-based monoatomic alloy electrocatalyst comprises the following steps:
(1) Mixing water, a copper metal precursor, a reducing agent, hexadecyl trimethyl ammonium bromide and hexamethylenetetramine to obtain a mixed solution;
the copper metal precursor in the step (1) is copper nitrate or a hydrate of copper nitrate; the reducing agent is ascorbic acid;
(2) Heating the mixed solution obtained in the step (1) to perform a reduction reaction to obtain copper nano sheets mainly comprising (111) crystal faces;
the temperature of the reduction reaction in the step (2) is 60-100 ℃, and the time of the reduction reaction is 0.5-5 h;
(3) Mixing the copper nano-sheets obtained in the step (2) with water to obtain a copper nano-sheet aqueous solution;
(4) Under inert atmosphere, adding a noble metal precursor into the copper nano sheet aqueous solution obtained in the step (3) to carry out galvanic replacement reaction to obtain copper-based monoatomic alloy Pd 0.06 A Cu electrocatalyst;
the noble metal precursor is added in the form of an aqueous solution; the noble metal precursor in the step (4) is palladium nitrate;
the molar ratio of the noble metal precursor to the copper nano-sheet in the copper nano-sheet aqueous solution in the step (4) is 1: (10-20).
2. The method according to claim 1, wherein the mass ratio of the copper metal precursor to the reducing agent in the step (1) is 1: (1.8-2.5).
3. The preparation method of claim 1, wherein the mass ratio of hexadecyl trimethyl ammonium bromide to hexamethylenetetramine in the step (1) is 1 (0.8-1.2); the mass ratio of the cetyl trimethyl ammonium bromide to the copper metal precursor in the step (1) is (1.8-2.5): 1.
4. the method according to claim 1, wherein the mass-to-water volume ratio of the copper nanoplatelets in the step (3) is 10mg: (15-25) mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211322528.1A CN115595618B (en) | 2022-10-27 | 2022-10-27 | Copper-based monoatomic alloy electrocatalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211322528.1A CN115595618B (en) | 2022-10-27 | 2022-10-27 | Copper-based monoatomic alloy electrocatalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115595618A CN115595618A (en) | 2023-01-13 |
| CN115595618B true CN115595618B (en) | 2023-05-16 |
Family
ID=84850723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211322528.1A Active CN115595618B (en) | 2022-10-27 | 2022-10-27 | Copper-based monoatomic alloy electrocatalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115595618B (en) |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100507088C (en) * | 2006-02-20 | 2009-07-01 | 清华大学 | Method for preparing palladium carried metal-based electrode used for electro-catalysis of chlore-aromatics for dechlorination |
| US20110195347A1 (en) * | 2010-02-05 | 2011-08-11 | Basf Se | Process for producing a catalyst and catalyst |
| CN103334121B (en) * | 2013-07-09 | 2015-10-14 | 北京工业大学 | The preparation method of the auxiliary Pd-Cu/Ti electrode of a kind of CV scanning and application |
| CN104923254B (en) * | 2015-05-28 | 2017-03-01 | 中国科学技术大学 | A kind of cuprio noble metal catalyst, its preparation method and application |
| CN105845948B (en) * | 2016-04-07 | 2018-02-27 | 河南师范大学 | A kind of preparation method of flower-shaped copper/cupric oxide Micron-nano composites carried noble metal fuel-cell catalyst |
| US11131031B2 (en) * | 2018-06-12 | 2021-09-28 | Honda Motor Co., Ltd. | High-yield preparation of two-dimensional copper nanosheets |
| CN109225253B (en) * | 2018-08-09 | 2020-07-17 | 厦门大学 | Atomic-level dispersed palladium-copper catalyst, and preparation method and catalytic application thereof |
| US11458538B2 (en) * | 2018-11-19 | 2022-10-04 | Honda Motor Co., Ltd. | General synthetic strategy for fabrication of multi-metallic nanostructures |
| CN110075843B (en) * | 2019-04-08 | 2020-03-24 | 电子科技大学 | Nano copper catalyst, preparation method thereof and application thereof in synthesis of acetic acid or ammonia |
| CN114054023B (en) * | 2020-07-31 | 2023-08-25 | 中国科学院大连化学物理研究所 | Preparation method and application of alloy monoatomic catalyst |
| CN113020614B (en) * | 2021-02-26 | 2022-09-02 | 中国科学技术大学 | Copper-based monatomic alloy catalyst, preparation method and application thereof, and membrane electrode electrolyte battery for preparing formic acid through carbon dioxide electroreduction |
| CN113279013B (en) * | 2021-05-24 | 2021-12-21 | 北京化工大学 | Monoatomic alloy nanowire catalyst for carbon dioxide electroreduction and preparation method thereof |
-
2022
- 2022-10-27 CN CN202211322528.1A patent/CN115595618B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN115595618A (en) | 2023-01-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112007681B (en) | Preparation method and application of nitrogen-doped biochar-loaded monoatomic iron | |
| CN101305485B (en) | Electrocatalyst for fuel cell and method for preparing the same | |
| US20080182745A1 (en) | Supported platinum and palladium catalysts and preparation method thereof | |
| CN107252705B (en) | Catalyst for electrochemical reduction of carbon dioxide and preparation method thereof | |
| CN111437864B (en) | High-dispersion Cu/NC nano-cluster catalyst and preparation method thereof | |
| CN112479317B (en) | Preparation method and application of composite cathode integrating efficient in-situ hydrogen peroxide electrosynthesis and catalytic performance | |
| US10003084B2 (en) | Metal nanoparticle-graphene composites and methods for their preparation and use | |
| Tsang et al. | Pd-Pt loaded graphene aerogel on nickel foam composite as binder-free anode for a direct glucose fuel cell unit | |
| WO2012071709A1 (en) | Ag/mnyox/c catalyst, preparation and application thereof | |
| CN108550871B (en) | Manganese dioxide/carbon black composite material and preparation method and application thereof | |
| WO2022032340A1 (en) | Catalyst | |
| CN108520965A (en) | A kind of preparation method of platinum-noble metal-copper ternary alloy nano hollow cube | |
| CN110571440B (en) | FeN4-CNT oxygen reduction catalyst preparation method | |
| CN115595618B (en) | Copper-based monoatomic alloy electrocatalyst and preparation method and application thereof | |
| CN113422080A (en) | Preparation method and application of carbon-supported non-platinum palladium-ruthenium-tungsten alloy nanoparticle electrocatalyst for alkaline hydrogen oxidation | |
| CN115180690B (en) | Nitrogen-doped graphene coated metal copper nano catalyst and preparation method thereof | |
| CN115532317B (en) | Pd/ZIFs-8@Ti 3 C 2 T x Electrocatalyst, preparation method and application thereof | |
| CN114381743B (en) | Composite hydrogen evolution catalyst and preparation method and application thereof | |
| CN116116411B (en) | Preparation method and application of biomass carbon-loaded copper-iron bimetallic oxide | |
| CN113373345B (en) | Supported superfine PtCoP ternary alloy nanoparticle for electrocatalytic methanol oxidation and preparation method thereof | |
| CN114394580B (en) | Self-supporting cobalt phosphide nanowire electrode and preparation method and application thereof | |
| CN114100630B (en) | Platinum-cobalt bimetallic nanoflower catalyst and preparation method and application thereof | |
| JP2001205086A (en) | Method for manufacturing platinum/ruthenium alloy- bearing catalyst | |
| CN117039020B (en) | Graphite carbon nano sheet loaded nitride fuel cell catalyst and preparation method thereof | |
| CN114588915B (en) | Supported platinum-based catalyst and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |